Aminecarbotrithioates and preparation

ABSTRACT

A thiolsulfonate is reacted with an aminecarbodithioate salt to given an aminecarbotrithioate product. The products of this invention have biological activity, particularly in controlling microorganisms and other pests.

This application is a divisional application of U.S. Pat. applicationSer. No. 166,258, filed July 26, 1971, now U.S. Pat. No. 3,810,890,issued May 14, 1974, which is a continuation-in-part of U.S. Pat.application Ser. No. 682,511, filed Nov. 13, 1967 now abandoned.

BACKGROUND OF THE INVENTION

This invention concerns a process for making aminecarbotrithioates byreaction between a thiosulfonate and an aminecarbodithioate salt,advantageously an alkali metal or ammonium salt. The reaction is carriedout advantageously in the presence of one or more organic liquids inwhich either or both of the reactants is dissolved or suspended, and ata temperature ranging between about 20° and about 150° C., if desiredunder an inert atmosphere, e.g., nitrogen. The invention also concernscertain novel aminecarbotrithioates. The aminecarbotrithioates havebiological activity, particularly in controlling microorganisms andother pests.

SUMMARY OF THE INVENTION

The process of this invention is represented by the following equations:##STR1## and ##STR2## wherein R₁, R₂, R₃ and R₄ are defined below, togive the mono- and bis-aminocarbotrithioate products hereinafter shown.

The process of this invention gives rise to the following products,indicated by Formulas I-VI, as represented by the following equation:##STR3## wherein R₁ represents alkenyl, loweralkyl- or halo-substitutedalkenyl, 2-(loweralkoxy)ethyl, 2-(aryloxy)ethyl or propargyl, R₂represents loweralkyl, aryl or loweralkyl or halo-substituted aryl andwherein R₃ and R₄ individually represent loweralkyl or hydrogen andtogether represent the remaining portion of a heterocyclic ringcontaining the nitrogen atom; ##STR4## wherein n represents an integerfrom 1, to 2, to 3, to 4, to 5, to 6, to 7, to 8, to 9, to 10, to 11, to12, and wherein R₃ and R₄ individually represent loweralkyl or hydrogenand together represent the remaining portion of a heterocyclic ringcontaining the nitrogen atom; ##STR5## wherein R₃ and R₄ individuallyrepresent loweralkyl or hydrogen and together represent the remainingportion of a heterocyclic ring containing the nitrogen atom; wherein nrepresents 0 or 1; wherein each Z₃ may be the same or different andrepresents loweralkyl, hydrogen, chloro, bromo, iodo, loweralkoxyl,nitro or loweralkylthio; and wherein m is 1, to 2, to 3, to 4, not morethan two Z₃ groups of which are iodo or nitro; ##STR6## wherein R₃ andR₄ individually represent loweralkyl or hydrogen and together representthe remaining portion of a heterocyclic ring containing the nitrogenatom; R₅ represents loweralkyl, phenyl, loweralkylphenyl, halophenyl orloweralkoxyphenyl; n is 1, to 2 and X is O or S; ##STR7## wherein R₃ andR₄ individually represent loweralkyl or hydrogen and together representthe remaining portion of a heterocyclic ring containing the nitrogenatom; and wherein n is 10, to 11, to 12, to 13, to 14, to 15, to 16, to17, to 18, to 19, to 20; ##STR8## wherein R₃ and R₄ individuallyrepresent loweralkyl or hydrogen and together represent the remainingportion of a heterocyclic ring containing the nitrogen atom.

As used in the specification and claims, the terms "loweralkyl" and"loweralkoxy" designate alkyl and alkoxy groups having from 1 to 4carbon atoms, such as, for example, methyl, ethyl, propyl and butyl; andmethoxy, ethoxy, propoxy and butoxy, respectively.

DETAILED DESCRIPTION OF THE INVENTION

The process of this invention can be represented by the followingequation for the monoaminecarbotrithioate Formula (I) compounds, thereaction involved being equally operable in the preparation of Formula(II)-(VI) compounds: ##STR9## wherein M⁺ = alkali metal or ammoniumcation

R₂ = loweralkyl, aryl or substituted aryl

R₁ = alkenyl, substituted alkenyl, 2-(loweralkylthio)ethyl,2-(arylthio)ethyl, 2-(loweralkoxy)ethyl, 2-(aryloxy)ethyl or propargyland wherein R₃ and R₄ represent the remaining portion of a heterocyclicring containing the nitrogen atom.

In the reaction, a single organic liquid or a mixture of two immiscibleorganic liquids or a mixture of a water immiscible liquid and water maybe used as the reaction medium. For instance, the thiolsulfonatereactant may be dissolved in a water-immiscible solvent such asmethylene chloride, chloroform, ethyl ether, benzene, toluene, xylene orcommercial chlorinated solvents, and the carbodithioate salt may bedissolved in water. The two solutions are then mixed and vigorouslyagitated for a period of time from 5 minutes to 20 hours advantageouslyat a temperature ranging between 20° and 150° C. Again, both reactantsmay be completely soluble in a single organic solvent, or only onereactant may be completely soluble in the single organic liquid orneither reactant may be completely soluble in the single organic liquid.For another example, a solution of the thiolsulfonate in ethanol can beadded to a suspension of the carbodithioate salt in ethanol, and theresulting mixture stirred at the required temperature to cause reaction.Solvents useful in single organic liquid systems include ethanol,methanol, isopropanol, acetone, methylethylketone, methylene chloride,chloroform, benzene, toluene, or xylene. When operating above theboiling point of the solvent system, a pressure vessel is advantageouslyused.

The amounts of the reactants to be employed in the reaction are notcritical, some of the desired products being obtained when the reactantsare employed in any proportions. In a preferred method, good yields areobtained when employing substantially stoichiometric proportions of thereactants. Bis(aminecarbotrithioates) are advantageously prepared byreacting two equivalents of an aminecarbodithioate, for example, sodium4-morpholinecarbodithioate, with one equivalent of a thiolsulfonate, forexample, 2,2'-bis(phenylsulfonylthio)diethyl sulfide to givethiodiethylene bis(morpholinecarbotrithioate). Up to 100 percent excessof either reactant is not deleterious, however.

Representative thiolsulfonates useful in the process of this inventioninclude o-nitrophenyl benzenethiolsulfonate, dinitrophenylbenzenethiolsulfonate 2,3,3-tribromoallyl p-toluenethiolsulfonate,2,3,3-tribromoallyl benzenethiolsulfonate, p-phenylenebis(methanethiolsulfonate), pentamethylene bis(methanethiolsulfonae)allyl p-toluenethiolsulfonate, α,α'-bis(methylsulfonylthio)-o-xylene,propargyl p-toluenethiolsulfonate, methyl methanethiolsulfonate,2-methylbenzyl benzenethiolsulfonate, ethyl p-toluenethiolsulfonate,n-dodecyl p-toluenethiolsulfonate, benzyl p-toluenethiolsulfonate,2-(methylthio)ethyl p-iodobenzenethiolsulfonate, 2-(methylthio)ethylmethanethiolsulfonate, 2,2'-bis(phenylsulfonylthio)diethyl sulfide,2-(ethylthio)ethyl methanethiolsulfonate, 2-(phenoxy)ethylbenzenethiolsulfonate, 2-phenylallyl methanethiolsulfonate,2,2'-bis(phenylsulfonylthio)diethyl sulfide and methylthiomethylmethanethiolsulfonate.

Representative aminocarbodithioate salts useful in the process of thisinvention include sodium, potassium, lithium and ammoniumdithiocarbamate, dimethylaminecarbodithioate,diethylaminecarbodithioate, 1-piperidinecarbodithioate, and4-morpholinecarbodithioate.

The novel compounds of this invention are particularly useful aspesticides for the control of various fungal and bacterial organisms andother pests such as Bacillus subtilis, Staphylococcus aureus,Escherichia coli, Candida albicans, Trichophyton mentagrophytes,Venturia inaequalis, Piricularia oryzae, Aerobacter aerogenes,Salmonella typhosa, Candida pelliculosa, Pullularia pullulans, Rhizopusnigricans, Aspergillus terreus, Eimeria necatrix, Eimeria tenella andDaphnia.

The following examples describe completely representative specificembodiments and the best modes contemplated by the inventors of carryingout their invention. Temperatures given are centigrade.

EXAMPLE 1 o-NITROPHENYL DIETHYLAMINECARBOTRITHIOATE ##STR10##

o-Nitrophenyl benzenethiolsulfonate (14.8 grams; 0.0500 mole) in 75milliliters of methylene chloride and 8.7 grams (0.0510 mole) of sodiumdiethylaminecarbodithioate in 75 milliliters of water were combined andstirred vigorously for 18 hours at room temperature. The organic layerwas separated, washed with water until free of water-soluble salts anddried over anhydrous magnesium sulfate. The solvent was removed byevaporation in vacuo, and the yellow, oily residue was crystallized(Norit) from 1:1 volumetric proportions of methylcyclohexane and benzeneto give golden platelets, melting point 92°-93°. Recrystallization fromthe same methylcyclohexane-benzene mixture gave the pure o-nitrophenyldiethylaminecarbotrithioate, melting point 92.5°-93°.

Anal. Calcd. for C₁₁ H₁₄ N₂ O₂ S₃ : C, 43.68; H, 4.67; N, 9.27; S,31.80. Found: C, 43.69; H, 4.64; N, 8.93; S, 32.07.

EXAMPLE 2 2,3,3-TRIBROMOALLYL 1-PIPERIDINECARBOTRITHIOATE ##STR11##

Sodium 1-piperidinecarbodithioate (6.7 grams; 0.033 mole) was added to asuspension of 15.0 grams (0.0330 mole) of 2,3,3-tribromoallylp-toluenethiolsulfonate in 250 milliliters of methanol with stirring atroom temperature. Dissolution of the reactants occurred immediately withconcomitant formation of a yellow-orange color. The mixture was stirredvigorously at room temperature for 1.75 hours, and the product,2,3,3-tribromoallyl 1-piperidinecarbotrithioate, was obtained as a lighttan solid, melting point 84°-86°. Two recrystallizations from ethanolgave the pure substance as white crystals, melting point 84.5°-86.5°.

Anal. Calcd. for C₉ H₁₂ Br₃ NS₃ : C, 23.0; H, 2.57; Br, 51.0. Found: C,23.0; H, 2.57; Br, 51.0.

EXAMPLE 3 2,3,3-TRIBROMOALLYL 4-MORPHOLINECARBOTRITHIOATE ##STR12##

Sodium 4-morpholinecarbodithioate (18.5 grams; 0.100 mole) was added inone portion to a solution of 45.1 grams (0.100 mole) of2,3,3-tribromoallyl benzenethiolsulfonate in 750 milliliters of methanolat room temperature with vigorous stirring. Stirring was continued for20 minutes, and the cream-colored precipitate which had formed wascollected on a filter, dried in vacuo and recrystallized from ethanol togive orange-brown crystals, melting point 112°-113.5°. A secondrecrystallization from ethanol gave the pure 2,3,3-tribromoallyl4-morpholinecarbotrithioate as tan crystals, melting point 112.5°-114°.

Anal. Calcd. for C₈ H₁₀ Br₃ NOS₃ : C, 20.4; H, 2.14; Br, 50.8. Found: C,20.4; H, 2.37; Br, 50.7.

EXAMPLE 4 PENTAMETHYLENE BIS(4-MORPHOLINECARBOTRITHIOATE) ##STR13##

A solution of 3.7 grams (0.020 mole) of sodium4-morpholinecarbodithioate in 25 milliliters of ethanol was added to asuspension of 2.9 grams (0.010 mole) of pentamethylenebis(methanethiolsulfonate) in 125 milliliters of ethanol. The reactionmixture was stirred at room temperature for 15 minutes, and theprecipitated white crystalline product was collected on a filter anddried. Recrystallization from ethanol gave the pure pentamethylenebis(4-morpholinecarbotrithioate) as colorless crystals, melting point83°-84.5°.

Anal. Calcd. for C₁₅ H₂₆ N₂ O₂ S₆ : C, 39.27; H, 5.71; S, 41.93. Found:C, 39.3; H, 5.48; S, 41.49.

EXAMPLE 5 ALLYL 1-PIPERIDINECARBOTRITHIOATE ##STR14##

A mixture of 16.5 grams (0.0726 mole) of allyl p-toluenethiolsulfonateand 13.3 grams (0.0725 mole) of sodium 1-piperidinecarbodithioate in 200milliliters of ethanol was heated at reflux temperature for one hour.The solvent was removed by evaporation in vacuo, leaving a mixture ofcrystalline material and oil. The mixture was slurried in ether andfiltered to remove the insoluble by-product, sodium p-toluenesulfinate.The ether was removed by evaporation in vacuo to give the crude productas an amber oil. The material was chromatographed on an acid-washedactivated alumina column, using 1:1 benzene-petroleum ether (boilingpoint 60°-70°). The pure allyl 1-piperidinecarbotrithioate was obtainedas a yellow oil, n_(D) ²⁵ 1.6339.

Anal. Calcd. for C₉ H₁₅ NS₃ : C, 46.31; H, 6.48; N, 6.00; S, 41.21.Found: C, 46.2; H, 6.56; N, 5.92; S, 41.70.

EXAMPLE 6 o-XYLYLENE BIS(4-MORPHOLINECARBOTRITHIOATE) ##STR15##

A mixture of 10.0 grams (0.0306 mole) ofα,α'-bis(methylsulfonylthio)-o-xylene and 11.3 grams of (0.0612 mole) ofsodium 4-morpholinecarbodithioate in 300 milliliters of ethanol wasstirred at room temperature for 30 minutes. The precipitate which formedwas collected by filtration and stirred with hot ethanol. Theethanol-insoluble crude product was collected on a filter, air-dried andrecrystallized from acetonitrile to give the pure o-xylylenebis(4-morpholinecarbotrithioate) as ivory-colored crystals, meltingpoint 174°-175°.

Anal. Calcd. for C₁₈ H₂₄ N₂ O₂ S₆ : C, 43.87; H, 4.91; N, 5.69. Found:C, 43.7; H, 4.70; N, 5.54.

EXAMPLE 7 PROPARGYL 4-MORPHOLINECARBOTRITHIOATE ##STR16##

A mixture of 9.0 grams (0.040 mole) of propargyl p-toluenethiolsulfonateand 7.4 grams (0.040 mole) of sodium 4-morpholinecarbodithioate in 300milliliters of ethyl ether was stirred at room temperature for 17 hours.During this period of time the by-product sodium p-toluenesulfinate hadprecipitated as white crystals and was removed by filtration. Thesolvent was removed from the filtrate by evaporation in vacuo, leavingan oily, red solid. The substance was dissolved in a minimum amount ofbenzene and precipitated by the addition of petroleum ether (boilingpoint 60°-70°) to give a yellow, crystalline, crude product.Recrystallization from isopropanol gave the pure propargyl4-morpholinecarbotrithioate as pale yellow crystals, melting point77°-78°.

Anal. Calcd. for C₈ H₁₁ NOS₃ : H, 41.2; H, 4.75; N, 6.00. Found: C,41.4; H, 5.12; N, 6.11.

EXAMPLE 8 METHYL DIETHYLAMINECARBOTRITHIOATE ##STR17##

A mixture of 41.0 grams (0.325 mole) of methyl methanethiolsulfonate,116.8 grams (0.0682 mole) of sodium diethylaminecarbodithioate, 400milliliters of methylene chloride and 25 milliliters of water wasstirred vigorously at room temperature for 48 hours. The methylenechloride layer was separated, washed with water and dried over anhydrousmagnesium sulfate. Removal of the solvent by evaporation in vacuo gavethe methyl diethylaminecarbotrithioate as a yellow oil, n_(D) ²⁵ 1.6111.The oil was crystallized at low temperature from a solution of ethylether and petroleum ether (boiling point 60°-70°) to give a low meltingyellow solid, which was quickly collected on a sintered glass Buechnerfunnel and dried in vacuo as a liquid in an Abderhalden drying pistol.The purified product, methyl diethylaminecarbotrithioate, was obtainedas a yellow oil, n_(D) ²⁵ 1.6118.

Anal. Calcd. for C₆ H₁₃ NS₃ : C, 36.9; H, 6.71; S, 49.23. Found: C,37.5; H, 6.91; S, 49.57.

EXAMPLE 9 o-NITROPHENYL 4-MORPHOLINECARBOTRITHIOATE ##STR18##

A solution of 16.0 grams (0.0865 mole) of sodium4-morpholinecarbodithioate in 50 milliliters of water was added to asolution of 25.1 grams (0.0850 mole) of o-nitrophenylbenzenethiolsulfonate in 250 milliliters of methylene chloride, and thereaction mixture was stirred vigorously at room temperature for fourhours. After standing at room temperature for an additional 13 hours,the methylene chloride layer was separated, washed with water and driedover anhydrous magnesium sulfate. The solvent was then removed byevaporation in vacuo, leaving the crude product as bright yellowcrystals. Two recrystallizations from ethanol gave the pureo-nitrophenyl 4-morpholinecarbotrithioate as yellow crystals, meltingpoint 158°-160°.

Anal. Calcd. for C₁₁ H₁₂ N₂ O₃ S₃ : C, 41.75; H, 3.82; N, 8.86. Found:C, 41.7; H, 3.87; N, 8.68.

EXAMPLE 10 o-NITROPHENYL 1-PIPERIDINECARBOTRITHIOATE ##STR19##

A solution of 20.1 grams (0.110 mole) of sodium1-piperidinecarbodithioate in 50 milliliters of water was added to asolution of 29.5 grams (0.100 mole) of o-nitrophenylbenzenethiolsulfonate in 200 milliliters of methylene chloride, and thereaction mixture was stirred at room temperature for 30 hours. Themethylene chloride layer was separated, washed with water and dried overanhydrous magnesium sulfate. The solvent was removed by evaporation invacuo, leaving the bright yellow, crystalline, crude product. Tworecrystallizations from acetonitrile gave the pure o-nitrophenyl1-piperidinecarbotrithioate as bright yellow crystals, melting point149.5°-151.5°.

Anal. Calcd. for C₁₂ H₁₄ N₂ O₂ S₃ : C, 45.84; H, 4.49; N, 8.91. Found:C, 45.8; H, 4.51; N, 8.84.

EXAMPLE 11 2-METHYLBENZYL DIMETHYLAMINECARBOTRITHIOATE ##STR20##

A mixture of 27.8 grams (0.100 mole) of 2-methylbenzylbenzenethiolsulfonate and 19.7 grams (0.110 mole) of sodiumdimethylaminecarbodithioate dihydrate in 300 milliliters of methanol wasstirred at room temperature for 20 hours. The white solid which hadformed was collected on a filter and dried. The crude substance wastwice recrystallized from ethanol to give the pure 2-methylbenzyldimethylaminecarbotrithioate as colorless crystals, melting point83°-85°.

Anal. Calcd. for C₁₁ H₁₅ NS₃ : C, 51.32; H, 5.87; N, 5.44. Found: C,51.3; H, 6.01; N, 5.33.

EXAMPLE 12 ETHYL DIMETHYLAMINECARBOTRITHIOATE ##STR21##

A mixture of 18.0 grams (0.0832 mole) of ethyl p-toluenethiolsulfonateand 16.4 grams (0.0915 mole) of sodium dimethylaminocarbodithioatedihydrate in 250 milliliters of methanol was stirred at room temperaturefor two hours. The solvent was then removed by evaporation in vacuo,leaving an oily residue which was slurried in ether and filtered toremove the insoluble by-product, sodium p-toluenesulfinate. The etherfiltrate was dried over anhydrous magnesium sulfate and evaporated todryness, leaving the crude product as a pale green oil. Treatment of asolution of the crude product in methylene chloride with activatedalumina, with subsequent filtration and evaporation of the solvent, gavethe ethyl dimethylaminecarbotrithioate as a pale yellow oil, n_(D) ²⁵1.6205. (Lit. n_(D) ²⁵ 1.6278; A. A. Watson, J. Chem. Soc., 1964, 2100).

EXAMPLE 13 n-DODECYL DIMETHYLAMINECARBOTRITHIOATE ##STR22##

A solution of 13.8 grams (0.0772 mole) of sodiumdimethylaminecarbodithioate dihydrate in 150 milliliters of methanol wasslowly added with stirring to a suspension of 25.0 grams (0.0702 mole)of n-dodecyl p-toluenethiolsulfonate in 150 milliliters of methanol. Thereaction mixture was stirred at room temperature for 16 hours duringwhich time the product precipitated. The white, crystalline precipitatewas collected on a filter and recrystallized from ethanol to give thepure n-dodecyl dimethylaminecarbotrithioate as colorless crystals,melting point 48°-50°.

Anal. Calcd. for C₁₅ H₃₁ NS₃ : C, 56.02; H, 9.72; N, 4.36. Found: C,56.3; H, 9.98; N, 4.37.

EXAMPLE 14 BENZYL DIMETHYLAMINECARBOTRITHIOATE ##STR23##

A solution of 17.8 grams (0.0640 mole) of benzyl p-toluenethiolsulfonatein 150 milliliters of methanol was added to a stirred suspension of 12.6grams (0.0700 mole) of sodium dimethylaminecarbodithioate dihydrate in150 milliliters of methanol, and the mixture was stirred at roomtemperature for 18 hours. During the reaction period the crude productprecipitated as white crystals and was collected on a filter. Thefiltrate was evaporated to dryness, and the residue was extracted withmethylene chloride, leaving the by-product, sodium p-toluenesulfinate,undissolved. The methylene chloride extract was concentrated to give afurther amount of the crude benzyl dimethylaminecarbotrithioate, whichwas combined with the first amount. Recrystallization from ethanol(Norit) gave the pure benzyl dimethylaminecarbotrithioate as long,colorless needles, melting point 86.5°-87°. (Lit. melting point 85°,U.S. Pat. No. 3,232,974, Imperial Chemical Industries, Ltd.).

Anal. Calcd. for C₁₀ H₁₃ NS₃ : C, 49.34; H, 5.38; N, 5.76. Found: C,49.35; H, 5.44; N, 5.40.

EXAMPLE 15 2-METHYLBENZYL 1-PIPERIDINECARBOTRITHIOATE ##STR24##

A solution of 24.1 grams (0.110 mole) of sodium1-piperidinecarbodithioate in 200 milliliters of methanol was added withstirring to a suspension of 27.8 grams (0.100 mole) of 2-methylbenzylbenzenethiolsulfonate in 100 milliliters of methanol. The formation of awhite precipitate was observed immediately. The reaction mixture wasallowed to stand at room temperature for 20 hours and was then filteredto collect the white, crystalline, crude product. Recrystallization fromisopropanol gave the pure 2-methylbenzyl 1-piperidinecarbotrithioate ascolorless crystals, melting point 103°-105°.

Anal. Calcd. for C₁₄ H₁₉ NS₃ : C, 56.56; H, 6.44; N, 4.71. Found: C,56.6; H, 6.55; N, 4.87.

EXAMPLE 16 2-(METHYLTHIO)ETHYL DIMETHYLAMINECARBOTRITHIOATE ##STR25##

A solution of 16.1 grams (0.0431 mole) of 2-(methylthio)ethylp-iodobenzenethiolsulfonate in 75 milliliters of methanol was added withstirring to a solution of 8.5 grams (0.047 mole) of sodiumdimethylaminecarbodithioate dihydrate in 75 millilters of methanol, andthe reaction mixture was stirred for 15 hours at room temperature. Thesolvent was removed by evaporation in vacuo, leaving a residue of whitesolid. The residue was extracted with methylene chloride and the sodiump-iodobenzenesulfinate by-product removed by filtration. The filtratewas concentrated to give the crude product as a white solid, which wascollected of a filter and recrystallized from methanol to give the pure2-(methylthio)ethyl dimethylaminecarbotrithioate as colorless needles,melting point 36°-37°.

Anal. Calcd. for C₆ H₁₃ NS₄ : C, 31.68; H, 5.76; N, 6.16. Found: C,31.7; H, 6.00; N, 5.93.

EXAMPLE 17 2-(METHYLTHIO)ETHYL DIMETHYLAMINECARBOTRITHIOATE

A solution of 10.6 grams (0.0592 mole) of sodiumdimethylaminecarbodithioate dihydrate in 100 milliliters of methanol waspurged of air by a stream of nitrogen. 2-(Methylthio)ethylmethanethiolsulfonate (10.0 grams., 0.0537 mole) in 100 milliliters ofmethanol was then added slowly with stirring at room temperature. Afterthe mixture had been stirred under nitrogen at room temperatureovernight the solvent was removed by evaporation in vacuo to leave anoily residue which, when shaken with methylene chloride, left a watermiscible layer which was separated from the organic phase and discarded.The methylene chloride solution was concentrated to give white crystals,melting point 35°-36°, with some remaining solid not completely meltinguntil a temperature of 105° was reached. A lengthy fractionalcrystallization procedure, using methanol as a recrystallizing solvent,gave the pure product as colorless needles, melting point 36°-37°. Amixture of this substance and a sample of the authentic substance gaveno depression of melting point.

EXAMPLE 18 2-(METHYLTHIO)ETHYL 4-MORPHOLINECARBOTRITHIOATE ##STR26##

A solution of 21.8 grams (0.118 mole) of sodium4-morpholinecarbodithioate in 150 milliliters of methanol was addedslowly at room temperature to a stirred solution of 20.0 grams (0.107mole) of 2-(methylthio)ethyl methanethiolsulfonate in 150 milliliters ofmethanol. Stirring was continued for 15 hours, and the solvent was thenremoved by evaporation in vacuo. The yellow oily residue was shaken withwater and the mixture extracted with methylene chloride. After theextract was dried over anhydrous magnesium sulfate the methylenechloride was removed by evaporation, leaving 27.0 grams of a turbid,yellow oil n_(D) ²⁵ 1.6473. Residual solvent was removed by vacuumdistillation, leaving 25.0 grams of yellow oil which was dissolved inmethylene chloride, the solution treated with activated charcoal andfiltered. Upon removing the methylene chloride in vacuo, the residue wasfound to consist of a clear, yellow oil, n_(D) ²⁵ 1.6445.

Anal. Calcd. for C₈ H₁₅ NOS₄ : C, 35.66; H, 5.61; N, 5.20. Found: C,35.4; H, 5.48; N, 5.43.

EXAMPLE 19 n-DODECYL 1-PIPERIDINECARBOTRITHIOATE ##STR27##

A solution of 9.7 grams (0.0440 mole) of sodium1-piperidinecarbodithioate in 150 milliliters of methanol was added withstirring to a suspension of 14.3 grams (0.0401 mole) of n-dodecylp-toluenethiolsulfonate in 150 milliliters of methanol at roomtemperature. A thick, white precipitate formed almost immediately. Thereaction mixture was allowed to stand at room temperature for 16.5hours. The mixture was then collected on a filter and dried. Tworecrystallizations from ethanol gave the pure product as white crystals,melting point 47.5°-49.5°.

Anal. Calcd. for C₁₈ H₃₅ NS₃ : C, 59.78; H, 9.75; N, 3.88. Found: C,59.8; H, 10.04; N, 4.14.

EXAMPLE 20 THIODIETHYLENE BIS(4-MORPHOLINECARBOTRITHIOATE) ##STR28##

Sodium 4-morpholinecarbodithioate (18.5 grams; 0.100 mole) was added toa warm, stirred solution of 21.7 grams (0.0500 mole) of2,2'-bis(phenylsulfonylthio)diethyl sulfide with the immediate formationof a voluminous, white precipitate. The reaction mixture was heatedunder reflux with stirring for 15 minutes and the white, crystallineproduct collected on a filter and washed with water to remove the sodiumbenzenesulfinate by-product. The crude product was recrystallized frommethanol to give a very pale yellow solid, melting point 116.5°-117.5°.A second recrystallization from methanol gave a pure product as paleyellow crystals, melting point 117°-117.5°.

Anal. Calcd. for C₁₄ H₂₄ N₂ O₂ S₇ : C, 35.27; H, 5.07; N, 5.88. Found:C, 35.2; H, 4.97; N, 5.79.

EXAMPLE 21 2-(METHYLTHIO)ETHYL DIETHYLAMINECARBOTRITHIOATE ##STR29##

To a stirred solution of 27.2 grams (0.121 mole) of sodiumdiethylaminecarbodithioate trihydrate in 100 milliliters of methanol wasslowly added a solution of 15.0 grams (0.0806 mole) of2-(methylthio)ethyl methanethiolsulfonate in 100 milliliters of methanolunder nitrogen. The reaction mixture was then stirred at roomtemperature under nitrogen for 18 hours. Evaporation of the solvent leftan oil which was washed with water. The water washings were combined andwashed with methylene chloride. The oil portion was added to themethylene chloride extract and the resulting solution dried overanhydrous magnesium sulfate. The solution was then treated withdecolorizing charcoal, filtered and concentrated in vacuo to give aclear, yellow oil, n_(D) ²⁵ 1.6137.

Anal. Calcd. for C₈ H₁₇ NS₄ : C, 37.57; H, 6.71; N, 5.48. Found: C,38.0; N, 6.69; N, 5.40.

EXAMPLE 22 2-(ETHYLTHIO)ETHYL 4-MORPHOLINECARBOTRITHIOATE ##STR30##

A mixture of 11.0 grams (0.055 mole) of 2-(ethylthio)ethylmethanethiolsulfonate and 12.2 grams (0.066 mole) of sodium4-morpholinecarbodithioate in 300 milliliters of methanol was stirred atroom temperature for 18 hours. The solvent was removed in vacuo, leavingan oily, crystalline mass which was stirred in ether and filtered toremove the insoluble by-product. The filtrate was dried over anhydrousmagnesium sulfate and was evaporated to dryness to give a yellow oil.The oil was crystallized by cooling in a dry-ice-methylene chloride bathand recrystallized from methanol. Two recrystallizations fromisopropanol gave the pure substance as colorless crystals, melting point31°-32.5°.

Anal. Calcd. for C₉ H₁₇ NOS₄ : C, 38.13; H, 6.05; N, 4.95. Found: C,38.0; H, 5.85; N, 4.96.

EXAMPLE 23 2-PHENOXYETHYL 4-MORPHOLINECARBOTRITHIOATE ##STR31##

A solution of 15.1 grams (0.0816 mole) of sodium4-morpholinecarbodithioate in 150 milliliters of methanol was added withstirring to a suspension of 20.0 grams (0.0680 mole) of 2-(phenoxy)ethylbenzenethiolsulfonate in 150 milliliters of methanol. A thick, whiteprecipitate began forming immediately. The reaction mixture was stirredat room temperature for 19 hours, and the precipitate was collected on afilter. Recrystallization of product from methanol gave the puresubstance as colorless crystals, melting point 89°-91°.

Anal. Calcd. for C₁₃ H₁₇ NO₂ S₃ : C, 49.49; H, 5.43; N, 4.44. Found: C,49.2; H, 5.50; N, 4.47.

EXAMPLE 24 2-PHENYLALLYL 4-MORPHOLINECARBOTRITHIOATE ##STR32##

A solution of 16.7 grams (0.0732 mole) of 2-phenylallylmethanethiolsulfonate and 16.3 grams (0.0878 mole) of sodium4-morpholinecarbodithioate in 300 milliliters of methanol was stirred atroom temperature for 28 hours. The solvent was removed in vacuo, leavinga yellow residue which was stirred in ether and filtered to remove theinsoluble by-product, sodium methanesulfinate. The ether filtrate wasdried over anhydrous magnesium sulfate and evaporated to dryness toobtain a yellow, viscous oil. Trituration with a small amount of coldether gave the crude, crystalline product which was collected on afilter. Recrystallization of product from ethanol gave the puresubstance as colorless crystals, melting point 69.5°-71°.

Anal. Calcd. for C₁₄ H₁₇ NOS₃ : C, 53.98; H, 5.51, N, 4.50. Found: C,54.0; H, 5.38; N, 4.31.

EXAMPLE 25 THIODIETHYLENE BIS(DIMETHYLAMINECARBOTRITHIOATE) ##STR33##

Sodium dimethylaminecarbodithioate dihydrate (14.2 grams; 0.0792 mole)was added to a warm, stirred solution of 17.2 grams (0.0396 mole) of2,2'-bis(phenylsulfonylthio)diethyl sulfide in 700 milliliters ofmethanol. The mixture was heated under reflux with stirring for onehour, after which time the methanol was removed by evaporation in vacuo.The solid residue was extracted with water at room temperature to removethe by-product, sodium benzenesulfinate, collected on a filter and driedin vacuo over calcium chloride. Two recrystallizations from ethylacetate gave the pure substance as colorless crystals, melting point105°-105.5°.

Anal. Calcd. for C₁₀ H₂₀ N₂ S₇ : C, 30.58; H, 5.13; N, 7.14. Found: C,30.6; H, 5.10; N, 7.25.

EXAMPLE 26 METHYLTHIOMETHYL 4-MORPHOLINECARBOTRITHIOATE ##STR34##

A solution of 13.0 grams (0.0700 mole) of sodium4-morpholinecarbodithioate in 125 milliliters of methanol was added to asolution of 10.0 grams (0.0580 mole) of methylthiomethylmethanethiolsulfonate in 125 milliliters of methanol, and the reactionmixture was stirred at room temperature for 16 hours. The whiteprecipitate, which had formed during the reaction period, was collectedon a filter and recrystallized from methanol to give the puremethylthiomethyl 4-morpholine carbotrithioate as pale yellow crystals,melting point 55°-57°.

Anal. Calcd. for C₇ H₁₃ NOS₄ : C, 32.88; H, 5.13; N, 5.49. Found: C,33.1; H, 4.81; N, 5.41.

The compounds of the present invention are variously useful aspesticides for the control of various bacteria, fungi, mollusks,crustaceans, insects and terrestial plants. For such use, the unmodifiedcompounds can be employed. Alternatively, the compounds can be dispersedon an inert finely divided solid and the resulting preparation employedas a dust. Also, such compounds or dust compositions containing saidcompounds can be dispersed in water with or without the aid ofadditional wetting agents and the resulting aqueous dispersions employedas sprays. In other procedures, the compounds can be employed assolutions in petroleum distillates or in other solvents or asconstituents of oil-in-water or water-in-oil emulsions. Such liquidcompositions can be employed as sprays, drenches or washes.

In representative operations, the compound of Example 2 gives goodcontrol of nymphal American cockroaches. In the test method, a papercylindrical cage is provided, fitted on the bottom with a number 52Whatman filter paper and on the top with retaining screen. Twenty-fivenymphal cockroaches are inactivated with CO₂ and immersed in an aqueousdispersion of 1,000 parts per million by weight of the compound ofExample 2 contained in the cage. The water is drawn off by suctionthrough the filter paper. The nymphs are then fed with sugar water andleft in the cage for three days, when a mortality count is made. Undersuch conditions, substantially complete control is attained. The samecompound is separately dispersed in a series of melted nutrient agarsamples to product a bacteriological culture medium containing 500p.p.m. thereof by weight of ultimate medium. Each of these media is thenpoured into a separate Petri dish and allowed to solidify. Thesolidified agar surface in each Petri dish is separately inoculated withone of Staphylococcus aureus, Bacillus subtilis, Aspergillus terreus,Candida pelliculosa, Pullularia pullulans or Salmonella typhosa, theinoculation being carried out by mopping the agar surfaces with a swabfrom a 24-hour broth culture of the organism. After 72 hours incubationat 30° C., the agar surface of each Petri dish is examined formicro-organisms. In each of the series, the control is 100 percent. Acontrol culture, to which none of the compound is added, shows vigorousgrowth.

The compound of Example 3 is similarly 100 percent effective againstStaphylococcus aureus and Bacillus subtilis at a concentration of 500p.p.m.

The compound of Example 5 is similarly effective against Staphylococcusaureus, Candida albicans and Trichophyton mentagrophytes, but at 100p.p.m. concentration. This compound is also effective in controllingDaphina and Carassius auratus when 100 p.p.m. of compound is dispersedin water containing these organisms. Piricularia oryzae is controlled100 percent by application of an aqueous dispersion containing 100p.p.m. of compound. Amaranthus species is 100 percent controlled byapplication to the soil of 10 lb./acre of the compound applied inaqueous dispersion as a drench to soil containing viable seed of saidspecies.

The compound of Example 7 is 100 percent effective against the Americancockroach at a concentration of 1000 p.p.m. used in the form of anaqueous dispersion. An aqueous dispersion of 150 p.p.m., when sprayed oncucumber plants and potato plants, respectively, gives 100 percentcontrol against Erysiphe cichoracearum and 95 percent control againstPhytophthora infestans.

The compounds of Example 24 is similarly 100 percent effective againstthe American cockroach and against Staphylococcus aureus at 500 p.p.m.and 100 percent effective against Candida albicans, Trichophytonmentagrophytes, Bacillus subtilis, Aspergillus terreus, Candidapelluculosa, Pullularia pullulans and Mycobacterium phlei, all at aconcentration of 100 p.p.m.

The following table shows effectiveness of other compounds at the statedconcentrations, using tests as described above.

    ______________________________________                                                  Effective for 100%                                                  Compound   Control of:     Concentration                                      ______________________________________                                        Example 6 Crabgrass        4,000 p.p.m.                                       Example 16                                                                              Daphnia          2 p.p.m.                                                     Ram's horn snail 2 p.p.m.                                                     Goldfish         2 p.p.m.                                                     Cucumber powder mildew                                                                         75 p.p.m.                                          Example 18                                                                              Daphnia          0.4 p.p.m.                                                   Goldfish         2 p.p.m.                                                     Cucumber powdery mildew                                                                        150 p.p.m.                                                   Apple scab fungus                                                                              400 p.p.m.                                                   S. aureus        100 p.p.m.                                                   E. Coli          100 p.p.m.                                                   C. albicans      100 p.p.m.                                                   T. mentagrophytes                                                                              100 p.p.m.                                                   B. subtilis      100 p.p.m.                                                   A. aerogenes     100 p.p.m.                                                   A. terreus       10 p.p.m.                                                    C. pelliculosa   100 p.p.m.                                                   P. pullulans     100 p.p.m.                                                   S. typhosa       100 p.p.m.                                         Example 21                                                                              E. Coli          500 p.p.m.                                                   C. albicans      100 p.p.m.                                                   T. mentagrophytes                                                                              100 p.p.m.                                                   B. subtilis      100 p.p.m.                                                   A. terreus       100 p.p.m.                                                   C. pelliculosa   100 p.p.m.                                                   P. pullulans     100 p.p.m.                                                   S. typhosa       100 p.p.m.                                         Example 22                                                                              S. aureus        500 p.p.m.                                                   C. albicans      500 p.p.m.                                                   T. mentagrophytes                                                                              100 p.p.m.                                                   B. subtilis      100 p.p.m.                                                   A. terreus       100 p.p.m.                                                   C. pelliculosa   100 p.p.m.                                                   p. pullulans     100 p.p.m.                                                   Bread mold fungus                                                                              500 p.p.m.                                         Example 5 S. aureus        500 p.p.m.                                                   T. mentagrophytes                                                                              500 p.p.m.                                                   B. subtilis      500 p.p.m.                                                   Bean mildew      100 p.p.m.                                         Example 19                                                                              S. sureus        100 p.p.m.                                                   T. mentagrophytes                                                                              100 p.p.m.                                                   P. pullulans     100 p.p.m.                                                   Ram's horn snail 2 p.p.m.                                           Example 4 Amaranthus spp.  25 lb./acre                                        Example 25                                                                              S. aureus        100 p.p.m.                                                   C. albicans      100 p.p.m.                                                   T. mentagrophytes                                                                              100 p.p.m.                                                   B. subtilis      100 p.p.m.                                                   A. terreus       100 p.p.m.                                                   C. pelliculosa   100 p.p.m.                                         ______________________________________                                    

What is claimed is:
 1. A compound corresponding to the formula R₄ R₃NC(═S)SS--CH₂ CH₂ --S--CH₂ CH₂ SSC(═S)NR₃ R₄ wherein R₃ and R₄individually represent loweralkyl or hydrogen or together with thenitrogen atom represent a piperidino or a morpholino group.
 2. Thecompound of claim 1 which is thiodiethylenebis(dimethylaminecarbotrithioate).
 3. The compound of claim 1 which isthiodiethylene bis(4-moropholinecarbotrithioate).